Baking enamel vehicle comprising the reaction product of phenol, formaldehyde and an oxazoline

ABSTRACT

An improved vehicle for the formulation of baking enamels obtained by reacting an oxazoline with a member selected from the group consisting of formaldehyde, and phenol.

United States Patent Hunsucker Aug. 28, 1973 BAKING ENAMEL VEHICLE COMPRISING [56] References Cited THE REACTION PRODUCT 0F PHENOL, UNITED STATES PATENTS FORMALDEHYDE AND AN OXAZOUNE 3,423,349 1/1969 Gagliardi 260/29.4 75 Inventor: Jerry Hoyt Humucker, Ten-e Haute 3,511,789 5/1970 shannon ct a1. 260/59 X Ind. 3,523,123 8/1970 Wehnncmer. 260/307 F 3,630,996 12/1971 Tomalia 260/59 X [73] Assignee: Commerclal Solvents Corporation, 3,640,957 2/1972 Tomalia et a1 260/59 X New York, NY. Primary Examiner-Howard E. Schain [22] 1971 Attorney-Howard E. Post, Robert H. Dewey et a1. [21] App]. No.: 185,430

Related US. Application Data 5: d E E l f b n improve ve we or e ormua mu 0 a mg [62] 2 2 5 36680 May 1970' enamels obtained by reacting an oxazoline with a member selected from the group consisting of formalde- 52 U.S. c1 260/57 R hyde and [51] Int. Cl C08g 5/06, COSg 9/24 5 Claims, No Drawings [58] Field of Search 260/59, 57 R BAKING ENAMEL VEHICLE COMPRISING THE REACTION PRODUCT OF PIIENOL, FORMALDEHYDE AND AN OXAZOLINE This is a division of application Ser. No. 36,680, filed May 12, 1970 now US. Pat. No. 3,654,229.

BACKGROUND OF THE INVENTION This invention relates to an improved vehicle for baking enamels. In a particular aspect, it relates to improved vehicles derived from oxazolines.

It is known from Purcell, US. Pat. No. 3,248,397, to prepare drying oils from 2-ethenyl oxazolines by copolymerizing them with olefinic or diolefinic monomers. These drying oils are useful as vehicles in protective coatings and finishes based on them have received wide acceptance. However, the protective coatings industry is ever in need of improved finishes, particularly baking enamels intended for use on steel. Particularly desirable are vehicles possessing corrosion resistance, good adhesion, hardness without loss of flexibility, and relatively colorless so as not to interfere with pigmentation of light-colored finishes.

A baking enamel is understood to be a partially polymerized resinous compound, usually dispersed in an organic solvent and formulated with pigments and other additives, which, when applied to a substratum and heated, polymerizes completely to form a tough, hard, adherent, flexible protective coating on the substratum.

SUMMARY OF THE INVENTION It is an object of this invention to provide improved vehicles for baking enamels.

Another object of this invention is to provide baking enamels based upon oxazoline co-polymers and terpolymers.

Other objects of this invention will be apparent to those skilled in the art from the disclosure herein.

It is the discovery of the present invention to provide polymeric resinous compounds having especial utility as the vehicle in the formulation of baking enamels. The resins of the present invention are condensation products of an oxazoline compound corresponding to formula I with a member selected from the group, herein designated as Group A, consisting of formaldehyde, melamine hexamethoxymethylmelamine, urea, ureaformaldehyde resin, phenol and 2,2-dimethylolpropionic acid, or mixtures thereof.

In the foregoing formula I, R can be a saturated or unsaturated hydrocarbon radical of from one to carbons or the group LII wherein X is any divalent, or trivalent saturated or unsaturated aliphatic hydrocarbon group, including straight chain or branched chain, of from one to 32 carbon atoms; R and R are hydrogen or hydroxymethyl and can be the same; R and R can be methyl, ethyl, hydroxymethyl or the acyloxymethyl group RCH COOCH wherein R is a saturated or unsaturated aliphatic hydrocarbon radical and can be the same as R; R and R can be the same or different; when X is divalent, R is hydrogen and when X is trivalent, R is the group wherein Y is a saturated or unsaturated hydrocarbon radical of 16 carbon atoms.

DETAILED DISCUSSION According to the present invention, there are provided new polymers and resins which, when incorporated in baking enamels, form hard, flexible, adherent films on a substratum, e.g. metals or textiles, after baking for a suitable period of time at a suitable baking temperature, e.g. about 20 minutes at 350F. When the substratum is a textile, e.g. a natural fiber, a waterproof fabric is obtained.

Generally the invention contemplates resinous compounds denoted Compounds B, Compounds D and Compounds E.

Compounds B are resinous compounds obtained by reacting with a member of Group A, or mixture of members thereof, an oxazoline corresponding to the above formula I wherein R is a saturated or unsaturated hydrocarbon radical of from 1 to 20 carbon atoms and R and R are hydrogen.

The oxazoline compounds useful in preparing the compound B correspond to the following formula II,

where B is a saturated or unsaturated hydrocarbon radical of from one to 20 carbon atoms; R and R are methyl, ethyl, hydroxymethyl or the acyloxymethyl group BCH,COOCI-I, and can be the same or different. Some of these compounds are commercially available or they can be prepared by reacting an alkanolamine corresponding to formula III,

with a monocarboxylic acid corresponding to the formula BCH COOH by known methods, e.g. by the method of Purcell, U.S. Pat. No. 3,336,145 which is incorporated herein by reference thereto. B has the same meaning described above; B and B can be methyl, ethyl or hydroxymethyl and can be the same or different. These alkanolamines include 2-amino-2-ethyl-l,3- propanediol (AEPD), 2-amino-2-methyl-l ,3- propanediol (AMPD), 2-amino-2-methyl-l-propanol (AMP), and tris(hydroxymethyl)aminomethane (TA).

The monocarboxylic acids suitable for forming the oxazoline compounds of formula 11 include saturated and unsaturated fatty acids of from two to 22 carbon atoms; including mixtures thereof. Such acids are wellknown in the art and include, but are not limited to, acetic, propionic, decanoic, lauric, linoleic, linolenic, oleic, stearic, behenic, etc. They are commercially available and the usual commercial grades, including the crude materials, are suitable for preparing the oxazoline compounds used in the preparation of Compounds B. When B or B (Formula ill) or both are hydroxymethyl, and when it is preferred that R and R (Formula ll) or both be acyloxymethyl, then sufficient acid is included to esterify the hydroxymethyl group or groups, as is known in the art.

Compounds B are prepared by reacting an oxazoline corresponding to the foregoing formula II:

a. with formaldehyde and melamine generally in a mole ratio of about 1:5:1 respectively,

b. with hexamethoxymethylmelamine generally in a mole ratio of about 2.5:] respectively;

c. with hexamethoxymethylmelamine and 2,2-dimethylolpropionic acid generally in a mole ratio of about 2:122 respectively.

The above ratios are not critical and can be varied within rather wide limits without departing from the concepts of the present invention. Generally, however, it is preferred that the amounts of reactants be within about i 20 percent of the ratios set forth above.

The reaction for preparing compounds B is conducted generally by dissolving the components in a suitable solvent, e.g. butanol, and heating at from about 90 to about 1 C under reflux for about 120 minutes, after which time the solvent and waterof reaction are removed by distillation. An acidic catalyst, many of which are known, e.g. p-toluene sulfonic acid, can be used when desired. Generally about 0.5 percent of catalyst based on the weight of reactants is sufficient.

Compounds D are resinous compounds obtained by reacting with a member of Group A, or mixture of members thereof, an oxazoline compound corresponding to the above formula I wherein R and R in the above formula are hydroxymethyl and R is a saturated or unsaturated hydrocarbon radical of one to car bon atoms.

The oxazoline compounds useful in preparing the compounds D correspond to the formula IV:

wherein D is a saturated or unsaturated hydrocarbon radical of from one to 20 carbon atoms; R and R have the same meaning defined hereinbefore and can be the same or different. These compounds can be prepared from the oxazolines of the foregoing formula ll by reacting them with formaldehyde in about 1:2 mole ratio at a temperature below about C, according to the method of H. L. Wehrmeister, U.S. Ser. No. 808,389, allowed but not issued, which is incorporated herein by reference thereto.

Compounds D are prepared by reacting an oxazoline corresponding to the foregoing formula IV:

a. with formaldehyde and melamine in a mole ratio of about 15:] respectively, or

b. with the hexamethoxymethylmelamine and dimethylolpropionic acid in a weight ratio of about 323:1 re spectively, or

c. with formaldehyde and urea in a mole ratio of about 1:3:] respectively, or

d. with a butylated or iso-butylated ureaformaldehyde resin in a weight ratio of about 1:] respectively, or

e. with the aforesaid urea-formaldehyde resin in a weight ratio of about 1:1 in the presence of dimethylolpropionic acid (DMPA) in a mole ratio of oxazoline to DMPA of about 1:1, or

f. with phenol preferably, but not necessarily, in the presence of an alkaline catalyst in a ratio of about l:12, respectively, or

g. with phenol and formaldehyde, preferably in the presence of an alkaline catalyst in a mole ratio of about l:4:l2 respectively.

The reaction for preparing compounds D is conducted generally by the process set forth above for compounds B.

The above ratios are not critical and can be varied within rather wide limits without departing from the concepts of the present invention. Generally, however, it is preferred that the amounts of reactants be within about i 20 percent of the ratios set forth.

Compounds E are resinous compounds obtained by reacting with a member of the Group A compounds an oxazoline corresponding to the above formula I where R corresponds to the group:

and R, R, R R, R and X have the definitions herein before set forth.

The oxazoline compounds useful in preparing compounds E are bis-oxazoline and tris-oxazoline obtained by the method of A. W. Campbell, et al, US. Pat. No. 3,419,520, which is incorporated herein by reference thereto. These compounds are derived by reacting an alkanolamine corresponding to the foregoing formula III with a dicarboxylic acid of from four to about 36 carbon atoms or with a tri-carboxylic acid of up to about 54 carbon atoms, respectively. There are obtained compounds corresponding to formula V where ais2or3andbis l orO:

Dicarboxylic acids suitable for preparing the compounds of formula V include, but are not limited to, acids of from four to carbon atoms, viz., succinic, glutaric, adipic, pimelic, suberic, azelaic, and sebacic. Also the dimer of C unsaturated fatty acids is a suitable and preferred dicarboxylic acid. Dimerized acids are known to those skilled in the art. They are described in, for example, Technical Bulletin No. 438C, published by Emery Industries, Inc., Cincinnati, Ohio.

The structure of dimer acid, shown schematically below, is essentially that of a long-chain dicarboxylic acid with two or more alkyl side chains (R and R-,). It appears to contain at least one ethylenic bond. Also within the molecule is the linkage at Z resulting from the polymerization of the two unsaturated fatty acid molecules that form dimer acid. The exact nature of the linkage is undetermined. It may be as simple as a single carbon-to-carbon bond, or as complex as a cyclic-structure. The total number of carbon atoms is 36.

The tricarboxylic acids suitable for preparing the compounds of formula V include the trimer of C unsaturated fatty acids. This trimerized acid is known to those skilled in the art and is described in the aforementioned Technical Bulletin No. 438C.

While not definitely established, the structure of trimer acid may be represented diagrammatically as shown below. It contains three or more alkyl side chains (R R R Within the molecule, at W, are undetermined linkages resulting from the polymerization of the three unsaturated fatty acid molecules that form trimer acid. The total number of carbon atoms is 54.

Compounds E are prepared by reacting a bisoxazoline or a tris-oxazoline corresponding to formula V:

a. with a urea-formaldehyde resin in about a 2:1 weight ratio, when the oxazoline is a tris-oxazoline or about a 121.2 when the oxazoline is a bis-oxazoline, respectively, or

b. with hexamethoxymethylmelamine in about a 1:0.4 weight ratio, or

c. with phenol in about a l:1l.5 mole ratio (about 10:] by wt.).

The above ratios are not critical and can be varied within rather wide limits without departing from the concepts of the present invention. Generally, however, it is preferred that the amounts of reactants be within about i percent of the ratios set forth.

The formaldehyde used in the present invention can be the 37 percent or 44 percent by weight aqueous solutions of commerce, or it can be provided by paraformaldehyde. Also suitable are the alcoholic solutions of formaldehyde.

The hexamethoxymethylmelamine used in preparing the compounds of the present invention is commercially available either as liquid or solid and both materials are suitable. Also commercially available are phenol, urea and 2,2-dimethylolpropionic acid. The usual commercial grades are suitable. Urea-formaldehyde suitable for the practice of this invention is commercially available and any of the usual commercial grades are satisfactory for use in the present invention. Butylated or di-butylated urea-formaldehyde, which on heating forms an irreversible resin, is preferred. The methylated or propylated products are also suitable.

The foregoing will be better understood with reference to the following examples. It is understood that the examples are presented for the purpose of illustration only, and it is not intended to be limited thereby.

PREPARATION AND PROPERTIES OF COMPOUNDS B EXAMPLE 1 The following ingredients were charged to a distillation kettle:

Melamine (0.48 mole) 60g Formaldehyde (203g of a 37% solution, 2.5 mole) 2-Ethyl-4-ethyl-4-propionyloxymethyl- 2-oxazoline (0.5 mole) l 12 Butanol ill The reactants were heated to reflux (about 94C) and maintained at that temperature for about 2 hours. Water and some butanol, as the azeotrope, 55 ml, were then removed by distillation and the reaction was again held under reflux for 15 minutes. Sufficient methanol was added to adjust the solids content to by weight and the system was cooled. The properties of the solution are given in Table l.

A wet film of 1.5 mil thickness was drawn down on a steel panel with a draw-down bar, then baked for 20 minutes at 350"F. The film had a pencil hardness of 6H and an impact resistance of 10 lb.

EXAMPLE 2 The following ingredients were charged to a distillation kettle and a reaction was carried out according to the general procedure of Example 1:

Hexarneth0xyrnethylmelamine'(0.286 mole) 9lg 2-Ethyl-4-ethyl-4-propionyloxymethyl- 2-oxazoline (0.74 mole) 159 TABLE 1 PROPERTIES OF COMPOUNDS B, POLYMER SOLUTIONS Ex. Visc- Solids No. Color osity Solvent Content,% 1 l Z-Z Methanol 80 2 3 B Ethoxy ethyl acetate 40 3 1 2 M-N Ethoxyethanol 50 Gardner EXAMPLE 3 An oxazoline corresponding to formula II was prepared from mixed fatty acids by charging 280g of tall oil fatty acids and 119g of 2-amino-2-ethyl-l,3- propanediol to a flask equipped with a stirrer, a reflux condenser and a take-off head. The mixture was heated to about 180C until the acid value was about 5. The total reaction time was about 4 hours. There was obtained an impure 2-hydrocarbo-4-ethyl-4- hydroxymethyl-Z-oxazoline wherein the hydrocarbo group was mixed C saturated and unsaturated aliphatic hydrocarbon groups. The product was used without further purification.

The following ingredients were charged to a distillation kettle and a reaction was carried out according to the general procedure of Example 1.

2-C, -4-Ethyl-4-hydroxymethyl-2-oxazoline (about 0.2 mole) 72g Dimethylolpropionic acid (0.2 mole) 26.8 Hexamethoxymethylmelamine (0.65 mole) 39.0

The reactants were mixed, then heated slowly to about 140C and 5 ml of methanol was removed by distillation to produce a polymer with an acid value of 37.36. It was then diluted to 50 percent with ethoxy ethanol. The properties of the resulting solution are given, in Table 1.

EXAMPLE 4 EXAMPLE 5 The experiment of Example 1 is repeated in all essential details except 0.5 mole of a 4,4-bis(hydroxymethyl- )oxazoline prepared from oleic acid and tris(hydroxymethyl)aminomethane in about a 1:1 mole ratio is substituted for the oxazoline of Example 1.

PREPARATION AND PROPERTIES OF COMPOUNDS D EXAMPLE 6 The following ingredients were charged to a distillation kettle equipped with a stirrer, a reflux condenser and a take-off head:

Melamine (0.48 mole) 60g Formaldehyde (203g of 37% solution, 2.5 mole 75 2-[ l ,1-Bis(hydroxymethyl)ethyl]-4-ethyl- 4-propionyloxymethyl-2-oxamline (0.5 mole) 136.5 l l l Butanol The reactants were mixed and heated with stirring to reflux temperature (about 95C) and held under reflux for 2 hours. During this time water from the formaldehyde and the water of reaction and some butanol were removed as the azeotrope (a total of 125g was removed over a period of about 50 minutes). The reaction product was then diluted to percent by weight with methanol. The properties of the solution are given in Table 1. A 1.5 mil thickness (wet) was drawn down on a steel panel with a draw-down bar, then baked for 20 minutes at 350F. The dried film was clear and colorless. The properties are given in Table 2.

EXAMPLE 7 The experiment of Example 6 was repeated in all essential details except that the solvent was omitted and the following materials were used:

Urea (0.5 mole) 30g Formaldehyde (121.5g of 37% solution, 1.5 mole) 45 2-{ 1,l-Bis(hydroxymethyl)ethyl1-4-ethyl- 4-propionyloxymethyl-2-oxazoline (0.5 mole) 136.5

The reactants were mixed and slowly heated to reflux with stirring, (about 35 minutes). The temperature was maintained at reflux (about C) for about 2 hours, then water was separated from the reaction mixture by distillation, resulting in final temperature of about :C as 66 m1 of water are removed. The reaction mixture was diluted to 80 percent solids with methanol and the properties of the solution were determined (Table 2). A 1.5 mil wet film was drawn down on a steel panel and baked for 20 minutes at 350F, giving a clear film. The properties are given in Table 3.

TABLE 2 PROPERTIES OF COMPOUNDS D, POLYMER SOLUTIONS Ex. Viscos- Solids No. Color ity Solvent Content,%

6 3 M-N Methanol 80 7 S Y-Z Methanol 80 8 5 Z L 100 9 4 D Ethoxy- 60 ethanol 10 5 X-Y Ethoxy- 66 ethanol 14 10 V-W Toluene 40 15 12 V Methanol 80 16 12 A-S Methanol 50 17 10 A-S Methanol 50 18 14 X Methanol 80 l9 10 F Methanol 67.5 20 3 G Butanol 80 Gardner TABLE 3 PROPERTIES OF COMPOUNDS D, BAKED FILMS Example Pencil Reverse Number Hardness Impact, Lb.

6 9H 10 7 9H 80+ 8 40+ 9 5H 60 10 4H 80 14 4H+ 80+ 15 4H 10 16 4B 17 9H The order of increasing hardness is B, F, HB, H, 3H, 4H, etc.

EXAMPLES 8-10 Following the general procedure of Example 6, the oxazoline of Example 6 was used to prepare additional resins. In Examples 8 and 9, the oxazoline was reacted with a butylated-urea resin (Beetle 1032 marketed by American Cyanamid Co.). In Example 9, there was included 2,2-dimethylo1propionic acid (DMPA) and 0.1g

hydrochloride of 2-amino-2-ethyl-1,3-propanediol catalyst. The resin of Example 10 is similar to that of Example 9 except that the butylated urea resin was replaced with hexamethoxymethylmelamine. Further details are listed in Table 4. The properties of the resin solutions obtained therefrom are given in Table 2. A 1.5 mil wet film was drawn down on steel and baked at 350F for the times shown in Table 4. The baked films were colorless and showed good solvent resistance. Ad-

ditional properties are given in Table 3.

TABLE 4 Example No. 8 9 l Oxuoline, g 54.6 54.6 91 Oxazoline, moles 0.2 0.2 0.33 Butylated urea, g 45.6 45.6 None DMPA, g none 268 44.6 DMPA, moles none 0.2 0.33 (analyst. g none 0.1 none Hexamethoxymethyl melamine. 1; none none 39 Hexamethoxymethyb melamine, moles none none 0.123 Reaction temp., C l50160 130 l-l H O removed, ml 16 7' 4- 5 Reaction time, min. 40 Film baked, min. 20

Includes butanol EXAMPLE 1 1 The experiment of Example 6 is repeated in all essential details except that 0.5 mole of 2-[1,1-

bis(hydroxymethyl)heptadecenyl]-4,4-hydroxymethyl- 2-oxazoline is substituted for the oxazoline of Example 6. The resulting resinous compound has utility as a vehicle in baking enamels.

EXAMPLE 12 The experiment of Example 8 is repeated in all essential details except that 0.5 mole of 2-[1,1-

bis(hydroxymethyl)nonyl]-4-methyl-4-hydroxymethyl- 2-oxazoline is substituted for the oxazoline of Example 8. The resulting resinous compound has utility as a vehicle in baking enamels.

EXAMPLE 13 The experiment of Example 10 is repeated in all essential details except that 0.5 mole of 2-[1,1- bis(hydroxymethyl)undecenyl]-4,4- dodecenyloxymethyl-Z-oxazoline is substituted for the oxazoline of Example 10. The resulting resinous compound is useful as a vehicle in baking enamels.

EXAMPLE 14 A 2-[1,1-bis(hydroxymethyl) oxazoline diester (I) was prepared by reacting tris(hydroxymethyl- )aminomethane, 1 mole, with 3 equivalents of tall oil fatty acids, then treating the oxazoline diester so formed with 2 moles of formaldehyde to form (I). This preparation is known in the art, as set forth hereinbefore. Phenol, 10.85g, (about 1.15 mole) and 1, 100g (about 1.05 mole) were mixed and heated to about 1 15C in about 15 minutes. The temperature was maintained at about 115C for about another 15 minutes and the product was allowed to cool. It was diluted to about 40 percent by weight with toluene. The properties of the solution are given in Table 2 and properties of the baked film are given in Table 3.

EXAMPLES 15-18 2-[ 1,1-Bis(hydroxymethyl)ethyl]-4-ethyl-4- 'l'AllLli 5 Uxuzoliml'ln-iml 'Jalal t lix. No. 5mins Moll: irmm .\lo]|- Gram 'l' xgw l5 54.13 0.2 18.8 0.2 2 11 P05 115 54.6 (1.2 15ml 0.2 X K011 17 27.3 0.1 22.8 0. 21 1.5 NaOll 18 54.6 0. 2 37. 0.4 2 NaUll 1 percent.

In Example 15, the mixture was heated at 160C for about 2.5 hours; in Example 16, the mixture was heated at 160C until the reaction was determined to be complete; in Example 17, the mixture was heated at 155C for about 45 minutes; in Example 18, the mixture was heated at 150160C for 2.5 hours and the resulting polymer provided a film having desirable characteristics when applied to a substratum and baked.

EXAMPLE 19 The oxazoline of Example 15 (68g, 0.25 mole) was reacted with 94g of phenol (1 mole) and 105g of 37 percent formaldehyde (1.3 mole) in the presence of 1.5g NaOH at C. The mixture was held at this temperature under reflux for 1 hour. The water was then separated by distillation; the reaction mixture was dissolved in methanol and neutralized to pH 7. The properties of the solution are given in Table 2.

A 1.5 mil film was drawn down on a steel panel and baked 20 minutes at 350F. The properties of the resulting coating are given in Table 3.

EXAMPLE 20 A I 2-[ 1,1-bis(hydroxymethyl)-hydrocarbo]-4,4- dimethyl-2-oxazoline was prepared from 2-amino-2- methyll-propanol mixed fatty acids and fonnaldehyde by known methods. The hydrocarbo group was PREPARATION AND PROPERTIES OF COMPOUNDS E EXAMPLE 21 A tris-oxazolinyl compound corresponding to formula V was prepared by mixing 259g,about 0.8 mole,

of trimerized fatty acid (Empol 1040 manufactured by Emery Industries, Inc., was used) with 85.4g, about 0.95 mole, of 2-amino-2-methyl-1-propanol. The mixture was then heated to 170-l75C with stirring until the acid value was 10. Water of reaction was separated in the take-off head. The total reaction time was about hours and the final acid value was 4.9.

A baking enamel was prepared using the following ingredients:

Tris-oxazoline 50g Butylated urea resin 25 Ferric oxide pigment 73.5 Talc 34.8 Calcium carbonate 34.8 Xylene 36.0 p-Toluene sulfonic acid catalyst 0.28 24% Lead drier 0.48 6% Cobalt drier 0.48

The above was drawn down on a steel panel and baked at 350F for 20 minutes. The properties are given in Table 6.

TABLE 6 PROPERTIES OF COMPOUNDS E, BAKED FILMS Example Pencil Reverse Number Hardness Impact, lb 21 HB 80 22 4H 80 23 4H 80+ 24 6H 30 25 B 80 26 3H 70 27 SH 80 28 H 80 36 F 80+ EXAMPLES 22-23 A bis-oxazoline compound corresponding to formula V was prepared by mixing 306g, about 1 mole, of dimerized C fatty acids with 119g, 1 mole of 2-arnino- 2-ethyl-1,3-propanediol, heating to 180-185C with stirring until the acid value was less than 5. The resulting product had a color, Gardner, of 14, a viscosity at 100% by wt. of Z and an acid value of 3.2.

This oxazoline was incorporated into two baking enamel formulas, as given below, which were drawn down on standard Q steel panels at 1.5 mil and baked for 20 minutes, 350F, to form in situ the resins which act as the binder in these fonnulations. The properties of the baked films are given in Table 6.

Ex. 22 Ex. 23 Oxazoline 87.9g 55.0g Melamine 34.2 Butylated urea resin 67.2 Ferric oxide 73.5 735 Calcium carbonate 34.8 34.8 Talc 34.8 34.8 Xylene 36 36.0 p-Toluene sulfonic acid 0.14 0.14 24% Lead drier 0.48 0.48 6% Cobalt drier 0.48 0.48

EXAMPLE 24 A bis-oxazoline corresponding to formula V was prepared by mixing 73g (0.5 moles) of adipic acid with 89.1g (1 mole) of 2-amino-2-methyl-1-propanol in a 3-necked flask equipped with a stirrer, a reflux condenser and a thermometer. The temperature was gradually raised to 200C over a 4 hour period at which time the acid value was reduced to 6.8.

To 3 parts of the above bis-oxazoline, 2 parts of hexamethoxymethylmelamine were added and a trace of p-toluene sulfonic acid as a catalyst. A 1.5 mil draw down was made on a standard Q panel and the panel was baked at 350F for 20 minutes to form a hard,

clear, solvent-resistant film. The properties of the film are given in Table 6.

EXAMPLES 25-26 A mixture of mono-oxazoline, bis-oxazoline and trisoxazoline correpsonding to formula V were prepared by mixing 153g (0.25 mole) of dimerized C fatty acid (which consisted of percent of the dimer, 22 percent of the trimer and 3 percent of monobasic acids) with 44.6g (0.5 mole) of 2-amin0-2-methyl-l-propanol.

The reactants were mixed in a flask equipped with stirrer, thermometer and nitrogen sparge. The temperature was raised to l-185C and maintained until the acid value was less than 10. The resulting oxazoline mixture was incorporated into two baking enamel formulas, as given below, which were then sprayed on standard Q steel panels at 1.5 mil thickness and baked at 350F for 20 minutes to form in situ the resins which act as the binders in these formulations. The properties of the baked films are given in Table 6. X-Component in Example 25 was butylated urea formaldehyde and in Example 26, it was hexamethoxymethylmelamine.

Mixed oxazolines 53.25g X-Component 39.00 Ferric oxide 73.5 Talc 34.8 Calcium carbonate 34.8 Xylene 36.0 p-Toluene sulfonic acid 0.28 24% Lead drier 0.48 6% Cobalt drier 0.48

EXAMPLES 27-28 A tris-oxazoline corresponding to formula V was prepared by mixing l19.lg (1 mole) of 2-amino-2-ethyl- 1,3-propanedi0l with 259.3g of trimerized C fatty acids (about 0.78 mole) and heating to 180-185C until the acid number was less than 5. The resulting product had a color of 8 and a viscosity, percent of Z -Z,.

The tris-oxazoline was incorporated into the following formulas and drawn down on standard Q panels at 1.5 mil thickness. The panels were then baked to form the in situ polymers which act as the binders for these formulations. The properties of the baked films are given in Table 6.

Ex. 27 Ex. 28 Tris-oxamline 81.6g 51.3g Melamine 41.7 Butylated urea resin 70.2 Ferric oxide 73.5 73.5 Calcium carbonate 34.8 34.8 Talc 34.8 34.8 Xylene 36.0 36.0 p-Toluene sulfonic acid 0.14 0. l4 24% Lead drier 0.48 0.48 6% Cobalt drier 0.48 0.48

EXAMPLE 29 The experiment of Example 24 is repeated except that TA, 1 mole, is substituted for AMP, and subenic acid, 0.5 mole, is substituted for adipic. The resinous compound so obtained has utility as a vehicle in a baking enamel.

EXAMPLE 30 The experiment of Example 24 is repeated except that AMPD, 1 mole, is substituted for AMP, and sebacic acid, 1 mole, is substituted for adipic acid. The resinous compound so obtained has utility as a vehicle in a baking enamel.

EXAMPLE 31 The experiment of Example 27 is repeated except that TA, 1 mole, is substituted for AEPD and 0.33 mole of trimerized fatty acid is substituted for 0.78 mole. The resinous compound so obtained has utility as a vehicle in a baking enamel.

EXAMPLE 32 The experiment of Example 31 is repeated except that 1 mole of trimerized fatty acid is substituted for 0.33 mole. The resinous compound so obtained has utility as a vehicle in a baking enamel.

EXAMPLE 33 The experiment of Example 27 is repeated except that 0.66 mole of trimerized fatty acid is substituted for 0.78 mole. The resinous compound so obtained has utility as a vehicle in a baking enamel.

EXAMPLE 34 A bis-oxazoline corresponding to formula V wherein R and R are hydroxymethyl was prepared by reacting 176g (about 0.25 mole) of the bis-oxazoline of 2- amino-Z-ethyl-1,3-propanediol and dimerized C fatty acids, prepared by known methods, with 33g (1 mole) of paraformaldehyde at 120C for 20 minutes and then at 150C for 30 minutes.

A 100g (0.13 mole) portion of the resulting tetrahydroxymethyl compound was reacted with 15g of phenol (0.17 mole) at 115C for 15 minutes. The reaction mixture was then cooled and diluted to 80 percent by weight solids with toluene. The viscosity of the solution was T and the color was 10.

A 1.5 mil wet film was drawn down on a steel panel and baked 20 minutes at 350F. The resulting film had a pencil hardness of F and a reverse impact of lb.

I claim:

1. A resinous compound consisting of the condensation product of phenol, formaldehyde and an oxazoline corresponding to the formula wherein R is a saturated or unsaturated hydrocarbon radical of from one to 20 carbon atoms; R and R are methyl, ethyl, hydroxymethyl or the acyloxymethyl group RCH COOCH said condensation product being effected in the presence of an alkaline catalyst.

2. The compound of claim 1 wherein R and R of said oxazoline are methyl groups.

3. The compound of claim 1 wherein R and R of said oxazaline are hydroxymethyl groups.

4. The compound of claim 1 wherein R and R of said oxazoline are represented by the formula RCH COOCH 5. The compound of claim 1 wherein R of said oxazoline is methyl or ethyl and R is represented by the formula RCH COOCH 

2. The compound of claim 1 wherein R3 and R4 of said oxazoline are methyl groups.
 3. The compound of claim 1 wherein R3 and R4 of said oxazaline are hydroxymethyl groups.
 4. The compound of claim 1 wherein R3 and R4 of said oxazoline are represented by the formula RCH2COOCH2-,
 5. The compound of claim 1 wherein R3 of said oxazoline is methyl or ethyl and R4 is represented by the formula RCH2COOCH2-. 